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Issue 1, 2004
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Preparation, characterisation and complexation of a redox-active, soft-donor macrocycle

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Abstract

Two new redox-active macrocycles 2 and 3 have been prepared based on an 18-membered S4N2–donor ring conjugated to one or two CpCo(dithiolene) redox/chromophore units respectively. Cyclic voltammetry for 2 showed one reversible reduction process at −0.29 V and EPR spectroscopy of the reduced form indicated a significant degree of delocalisation of the unpaired electron. The compound 2 showed an intense low-energy absorption at 675 nm (in CH2Cl2) that was shown to shift to higher energy during electrochemical reduction. Interaction of 2 with guest Ag(I) ions was followed by monitoring changes in the electrochemical and spectroscopic behaviour with sequential additions of the guest metal ion and by electrochemistry at a silver electrode. UV/Vis spectroscopic results indicated a strong interaction of Ag(I) with 2 involving large changes in the electronic nature of the macrocycle chromophore. Cyclic voltammetry also indicated interaction between 2 and Ag(I) and suggested the involvement of a film containing 2 on the electrode surface.

Graphical abstract: Preparation, characterisation and complexation of a redox-active, soft-donor macrocycle

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Publication details

The article was received on 04 Aug 2003, accepted on 05 Oct 2003 and first published on 31 Oct 2003


Article type: Paper
DOI: 10.1039/B309317D
Citation: New J. Chem., 2004,28, 98-103
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    Preparation, characterisation and complexation of a redox-active, soft-donor macrocycle

    H. J. Hartigan, G. Seeber, A. R. Mount, L. J. Yellowlees and N. Robertson, New J. Chem., 2004, 28, 98
    DOI: 10.1039/B309317D

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